5-phenylpyrimidines, their preparation, compositions comprising them and their use

ABSTRACT

5-Phenylpyrimidines of the formula I 
                         
in which the substituents and the index are as defined below:
     R 1 ,R 2  are hydrogen, alkyl, haloalkyl, cycloalkyl, halocycloalkyl, alkenyl, haloalkenyl, alkynyl or haloalkynyl, and R 1  and R 2  together with the nitrogen atom to which they are attached may also form a saturated or unsaturated ring which may be interrupted by an ether, thio, sulfoxyl or sulfonyl group and may be substituted by one to four groups R a  and/or R b ;   R 3  is hydrogen, halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy or alkenyloxy;   R 4  is hydrogen, halogen, cyano, hydroxyl, mercapto, azido, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, alkylthio, alkenylthio, alkynylthio, haloalkylthio, —ON═CR a R b , —CR c ═NOR a , —NR c N═CR a R b , —NR a R b , —NR c NR a R b , —NOR a , —NR c C(═NR c ′)NR a R b , —NR c C(═O)NR a R b , —NR a C(═O)R c , —NR a C(═NOR c )R c ′, —OC(═O)R c , —C(═NOR c )NR a R b , —CR c (═NNR a R b ), —C (═O)NR a R b  or —C(═O)R c ;
       in which R a , R b  and R c  are as defined in the description;   
       X is halogen, alkyl, alkoxy or haloalkyl; and   m is an integer from 1 to 5 ;
 
processes for preparing these compounds, compositions comprising them and their use for controlling harmful fungi are described.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This is a Divisional application of application Ser. No. 10/495,280, filed on May 11, 2004 (pending), the entire disclosure of which is herewith incorporated by reference, under 35 U.S.C. §371 as a national stage of International Application No. PCT/EP 02/12807, filed Nov. 15, 2002, the entire disclosure of which is herewith incorporated by reference.

The present invention relates to 5-phenylpyrimidine of the formula I

where the substituents and the index are as defined below:

-   R¹,R² independently of one another are hydrogen, C₁-C₆-alkyl,     C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl,     C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl or     C₂-C₆-haloalkynyl, -    R¹ and R² together with the nitrogen atom to which they are     attached may also form a saturated or unsaturated five- or     six-membered ring which may be interrupted by an ether-(—O—),     thio-(—S—), sulfoxyl-(—S[═O]—)or sulfonyl-(—SO₂—)group and/or may be     substituted by one to four groups R^(a) and/or R^(b);     -   R^(a),R^(b) independently of one another are hydrogen,         C₁-C₆-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₁-C₆-haloalkyl,         C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,     -    C₃-C₁₀-cycloalkyl, phenyl or a five- to ten-membered saturated,         partially unsaturated or aromatic heterocycle containing one to         four heteroatoms from the group consisting of O, N and S, where         the cyclic radicals may be partially or fully substituted by the         following groups R^(x):         -   R^(x) independently of one another are cyano, nitro, amino,             aminocarbonyl, aminothiocarbonyl, halogen, hydroxyl,             C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkyl-carbonyl,             C₁-C₆-alkylsulfonyl, C₁-C₆-alkylsulfoxyl, C₃-C₆-cycloalkyl,             C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkyloxycarbonyl,             C₁-C₆-alkylthio, C₁-C₆-alkylamino, di-C₁-C₆-alkylamino,             C₁-C₆-alkyl-aminocarbonyl, di-C₁-C₆-alkylaminocarbonyl,             C₁-C₆-alkylaminothiocarbonyl,             di-C₁-C₆-alkylamino-thiocarbonyl, C₂-C₆-alkenyl,             C₂-C₆-alkenyloxy, phenyl, phenoxy, benzyl, benzyloxy, 5- or             6-membered heterocyclyl, 5- or 6-membered hetaryl, 5- or             6-membered hetaryloxy, C(═NOR^(α)) —OR^(β)or             OC(R^(α))₂—C(R^(β))═NOR^(β),         -    where the cyclic groups for their part are unsubstituted or             substituted by one to three radicals R^(y):             -   R^(y) is cyano, nitro, halogen, hydroxyl, amino,                 aminocarbonyl, aminothiocarbonyl, C₁-C₆-alkyl,                 C₁-C₆-haloalkyl, C_(1-C) ₆-alkylsulfonyl,                 C₁-C₆-alkyl-sulfoxyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy,                 C₁-C₆-haloalkoxy, C₁-C₆-alkoxy-carbonyl,                 C₁-C₆-alkylthio, C₁-C₆-alkylamino, di-C₁-C₆-alkylamino,                 C₁-C₆-alkylaminocarbonyl, di-C₁-C₆-alkylaminocarbonyl,                 C₁-C₆-alkylamino-thiocarbonyl,                 di-C₁-C₆-alkylaminothiocarbonyl, C₂-C₆-alkenyl,                 C₂-C₆-alkenyloxy, C₃-C₆-cyclo-alkyl, C₃-C₆-cycloalkenyl,                 phenyl, phenoxy, phenylthio, benzyl, benzyloxy, 5- or                 6-membered heterocyclyl, 5- or 6-membered hetaryl, 5- or                 6-membered hetaryloxy or C(═NOR^(α))—OR^(β);             -   R^(α),R^(β)are hydrogen or C₁-C₆-alkyl;         -   R^(a) and R^(b) together, via an alkylene or alkenylene             chain with the bridging atom, may also form a saturated or             unsaturated 5- or 6-membered ring; -   R³ is hydrogen, halogen, cyano, C₁-C₆-alkyl, C₁-C₆-haloalkyl,     C₁-C₆-alkoxy, C₁-C₆-haloalkoxy or C₃-C₈-alkenyloxy; -   R⁴ is hydrogen, halogen, cyano, hydroxyl, mercapto, azido,     C₁-C₆-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₁-C₆-haloalkyl,     C₁-C₆-alkoxy, C₃-C₈-alkenyloxy, C₃-C₈-alkynyloxy, C₁-C₆-haloalkoxy,     C₁-C₆-alkylthio, C₃-C₈-alkenylthio, C₃-C₈-alkynylthio,     C₁-C₆-haloalkylthio, —ON═CR^(a)R^(b), —CR^(c)═NOR^(a),     —NR^(c)N═CR^(a)R^(b), —NR^(a)R^(b), —NR^(c)NR^(a)R^(b), —NOR^(a),     —NR^(c)C(═NR^(c)′)NR^(a)R^(b), —NR^(c)C(═O)NR^(a)R^(b),     —NR^(a)C(═O)R^(c), —NR^(a)C(═NOR^(c))R^(c′), —OC(═O)R^(c),     —C(═NOR^(c))NR^(a)R^(b), —CR^(c)(═NNR^(a)R^(b)), —C(═O)NR^(a)R^(b)or     —C(═O)R^(c);     -   R^(c) is one of the monovalent groups mentioned under R^(a) and         R^(b); -   x is halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy or C₁-C₆-haloalkyl; and -   m is an integer from 1 to 5.

Moreover, the invention relates to processes for preparing these compounds, to compositions comprising them and to their use for controlling harmful fungi.

Pyridylpyrimidine derivatives having fungicidal action are known from EP-A 407 899, DE-A 42 27 811 and WO-A 92/10490. Tetrahydropyrimidine derivatives having fungicidal action are known from GB-A 2 277 090.

The compounds described in the abovementioned publications are suitable for use as crop protection agents against harmful fungi.

However, in many cases their activity is unsatisfactory.

It is an object of the present invention to provide compounds having improved activity.

We have found that this object is achieved by the phenylpyrimidine derivatives I defined at the outset. Moreover, we have found processes for their preparation and compositions comprising them for controlling harmful fungi and their use for this purpose.

Compared to the prior-art compounds, the compounds of the formula I have increased activity against harmful fungi.

The compounds I can be obtained by different routes.

To prepare compounds of the formula I in which R⁴ is cyano or a group bound via a heteroatom, the starting materials used are advantageously sulfones of the formula II. In the formula II, the substituents X_(m) and R¹ to R³ are as defined in formula I and R is C₁-C₄-alkyl, preferably methyl.

The sulfones of the formula II are reacted under basic conditions with compounds of the formula III. For practical reasons, it is alternatively possible to employ directly the alkali metal, alkaline earth metal or ammonium salt of the compound III.

This reaction is usually carried out at temperatures of from 25° C. to 250° C., preferably from 40° C. to 210° C., in an inert organic solvent in the presence of a base [cf. DE-A 39 01 084; Chimia, 50, 525-530 (1996); Khim. Geterotsikl. Soedin, 12 1696-1697(1998).

Suitable solvents are halogenated hydrocarbons, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, dioxane, anisole and tetrahydrofuran, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide. Particular preference is given to ethanol, dichloromethane, acetonitrile and tetrahydrofuran. It is also possible to use mixtures of the solvents mentioned.

Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, and alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate and calcium carbonate. The bases are generally employed in catalytic amounts; however, they can also be employed in excess.

The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an up to 10-fold excess, in particular up to 3-fold excess, of III, based on II.

Compounds of the formula I in which R⁴ is hydrogen, alkyl, alkenyl, alkynyl or haloalkyl are advantageously obtained from phenylmalonic esters of the formula IV by reaction with amidines of the formula V.

This reaction is advantageously carried out under the conditions known from J. Chem. Soc. (1943) 388 and J. Org. Chem. 17 (1952), 1320.

Phenylmalonic esters of the formula IV are known from EP-A 10 02 788.

Hydroxypyrimidines of the formula VI are converted into halogen compounds VII [cf. J. Chem. Soc. (1943) 383; Helv. Chim. Acta 64 (1981), 113-152]. Suitable halogenating agents are in particular POCl₃ and POBr₃.

The halopyrimidines VII give, by reaction with amines VIII, compounds of the formula I.

This reaction is advantageously carried out under J. Chem. Soc. (1943) 383 and Chem. Eur. J. 5 (12) (1999), 3450-3458.

Phenylpyrimidines of the formula I in which R³ is cyano or a group attached via oxygen are advantageously obtained from the corresponding halogen compounds of the formula I by reaction with compounds IX under basic conditions. For practical reasons, it is alternatively possible to employ directly the alkali metal, alkaline earth metal or ammonium salt of the compound IX.

This reaction is usually carried out at temperatures of from 25° C. to 250° C., preferably from 40° C. to 210° C., in an inert organic solvent, if appropriate in the presence of a base [cf. Recl. Trav. Chim. Pays-Bas 61 (1942), 291; J. Heterocycl. Chem. 30 (4) (1993), 993-995].

Suitable solvents are ethers, sulfoxides, amides, particularly preferably dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, N,N-dimethylacetamide, diethyl ether, tetrahydrofuran and 1,2-dimethoxyethane. It is also possible to use mixtures of the solvents mentioned.

Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, and alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate and calcium carbonate.

The bases are generally employed in catalytic amounts; however, they can also be employed in excess.

Phenylpyrimidines of the formula I in which R³ is C₁-C₆-alkyl or C₁-C₆-haloalkyl are advantageously obtained from the corresponding halogen compounds of the formula I by reaction with organometallic compounds of the formula X in which M is a group Mg-Hal, Zn-R³ or B(OR)₂, where Hal is a halogen atom and R is hydrogen or C₁-C₄-alkyl and R³ is C₁-C₆-alkyl.

This reaction is usually carried out at temperatures of from −25° C. to 250° C., preferably from 0° C. to 150° C., in an inert organic solvent, if appropriate in the presence of a transition metal catalyst [vgl. Chem. and Pharm. Bull. 28 (2) (1980), 571-577; Tetrahedron Lett. 37 (8) (1996), 1309; Tetrahedron Lett. 35 (19) (1994), 3155; Synlett 7 (1999), 1145].

Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons and ethers, particularly preferably diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, benzene, toluene and xylene. It is also possible to use mixtures of the solvents mentioned.

Suitable transition metal catalysts are iron, cobalt, nickel, rhodium, platinum or palladium compounds, in particular nickel(0), nickel(II), palladium(0) and palladium(II) compounds. It is possible to use salts, such as palladium chloride or palladium acetate, or else Pd complexes. The only condition is that the palladium ligands can be replaced by the substrate under the reaction conditions.

The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an up to 10-fold, in particular up to 3-fold, excess of X, based on I.

The starting materials of the formula II required for preparing the compounds I can be obtained by methods known from the literature, for example by the following synthesis route:

starting from phenylmalonic acid alkyl esters of the formula XI and thiourea, compounds of the formula XII are obtained

where in formula XI R is C₁-C₆-alkyl. The reaction is usually carried out in a protic solvent, such as, for example, an alcohol, in particular ethanol, if appropriate in the presence of a base such as Na₂CO₃ or NaHCO₃. The reaction temperature is preferably 70-220° C. [cf. Collect. Czech. Chem. Commun. 48 (1983), 137-143; Heteroat. Chem. 10 (1999), 17-23; Czech. Chem. Commun. 58 (1993), 2215-2221].

The required phenylmalonic acid esters XI are known from EP-A 10 02 788.

Using alkylating agents XIII, compounds XII are converted into thiobarbituric acid derivatives. In the formula XIII, R is C₁-C₆-alkyl and X is a nucleophilically displaceable leaving group. Formula XIII represents, in a general manner, customary alkylating agents, such as methyl chloride and methyl bromide, dimethyl sulfate or methyl methanesulfonate.

The reaction can be carried out in water or else in a dipolar aprotic solvent, such as, for example, N,N-dimethylformamide [cf. U.S. Pat. No. 5,250,689]; it is preferably carried out in the presence of a base, such as, for example, KOH, NaOH, NaHCO₃ and Na₂CO₃ or pyridine. The reaction temperature is preferably 10-60° C.

Compounds XIV are converted into dichloropyrimidines of the formula XV [cf. EP-A 745 593; WO-A 99/32458; J.Org. Chem. 58 (1993), 3785-3786].

Suitable chlorinating agents [Cl] are, for example, POCl₃, PCl₃/Cl₂ or PCl₅. The reaction can be carried out in excess chlorinating agent (POCl₃) or in an inert solvent. This reaction is usually carried out at from 10 to 180° C.

By amination with XVI, the dichloro compounds of the formula XV are converted into the compounds of the formula XVII.

This reaction is preferably carried out at from 20 to 120° C. [cf. J. Chem. Res. S (7) (1995), 286-287; Liebigs Ann. Chem. (1995), 1703-1705] in an inert solvent, if appropriate in the presence of an auxiliary base, such as NaHCO₃, Na₂CO₃ or tert.amines.

The amines of the formula XVI are commercially available or known from the literature, or they can be prepared by known methods.

The thio compounds XVII are oxidized to the sulfones of the formula II.

The reaction is preferably carried out at from 10 to 50° C. in the presence of protic or aprotic solvents [cf.: B. Kor. Chem. Soc. 16 (1995), 489-492; Z. Chem. 17 (1977), 63]. Suitable oxidizing agents are, for example, hydrogen peroxide or 3-chloroperbenzoic acid.

The introduction of groups R³ different from chlorine into the sulfones II can be carried out analogously to the compounds of the formula I.

Compounds of the formula I in which R⁴ is —C(═O)R^(c), —C(═O)NR^(a)R^(b), —C(═NOR^(c))NR^(a)R^(b), —C(═NNR^(a)R^(b))R^(c) or —C(═NOR^(a))R^(c) are advantageously obtained from compounds of the formula I in which R⁴ is cyano.

Compounds of the formula I in which R⁴ is —C(═O)NR^(a)R^(b)or —C(═NOR^(c))NR^(a)R^(b)are from the corresponding nitriles (R⁴ ═cyano) by hydrolysis under acidic or basic conditions to give the carboxylic acids of the formula Ia and amidation with amines HNR^(a)R^(b). Hydrolysis is usually carried out in inert polar solvents, such as water or alcohols, preferably using inorganic bases, such as alkali metal or alkaline earth metal hydroxides, in particular NaOH.

These conversions are advantageously carried out under the conditions known from Chem. and Pharm. Bull. 30(12) (1982), 4314.

Compounds of the formula I in which R⁴ is —C(═NOR^(c))NR^(a)R^(b)are obtained from amides of the formula Ib by oximation with substituted hydroxylamines H₂N—OR^(c) under basic conditions [cf. U.S. Pat. No. 4,876,252]. The substituted hydroxylamines can be used as free base or, preferably, in the form of their acid addition salts. Particularly suitable are, for practical reasons, the halides, such as the chlorides, or the sulfates.

Alternatively, the amidoximes of the formula Ic in which R^(a) and R^(b) are hydrogen can also be obtained from the corresponding nitriles (R⁴=cyano) by reaction with hydroxylamine and subsequent alkylation. This reaction is advantageously carried out under the conditions known from DE-A 198 37 794.

Compounds of the formula I in which R⁴ is —C(═O)R^(c) can be obtained from the corresponding nitriles (R⁴=cyano) by reaction with Grignard reagents R^(c)-Mg-Hal where Hal is a halogen atom, in particular chlorine or bromine.

This reaction is advantageously carried out under the conditions known from J. Heterocycl. Chem. 31(4) (1994), 1041.

The substituents and indices in formulae Ia, Ib and Ic correspond to those in formula I.

Compounds of the formula I in which R⁴ is —C(═NNR^(a)R^(b))R^(c) can be obtained via the carbonyl compounds Id. They are obtained by reacting Id with hydrazines H₂NNR^(a)R^(b), preferably under the conditions known from J. Org. Chem. 31 (1966), 677.

Compounds of the formula I in which R⁴ is —C(═NOR^(a))R^(c) can be obtained by oximating carbonyl compounds Id. The oximation of Id is carried out analogously to the oximation of the compounds Ib.

The reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, chromatographic purification of the crude products. Some of the intermediates and end products are obtained in the form of colorless or slightly brownish, viscous oils which can be purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products can be obtained as solids, purification can also be carried out by recrystallization or digestion.

If individual compounds I are not obtainable by the routes described above, they can be prepared by derivatization of other compounds I.

In the definitions of the symbols given in the above formulae, collective terms were used which generally represent the following substituents:

-   halogen: fluorine, chlorine, bromine and iodine; -   alkyl: saturated, straight-chain or branched hydrocarbon radicals     having 1 to 4 or 6 carbon atoms, for example C₁-C₆-alkyl such as     methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl,     2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl,     2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl,     hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl,     2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,     1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,     2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,     1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl     and 1-ethyl-2-methylpropyl; -   haloalkyl: straight-chain or branched alkyl groups having 1 to 6     carbon atoms (as mentioned above), where in these groups some or all     of the hydrogen atoms can be replaced by halogen atoms as mentioned     above, for example C₁-C₂-haloalkyl such as chloromethyl,     bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl,     difluoromethyl, trifluoromethyl, chlorofluoromethyl,     dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl,     1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,     2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,     2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,     2,2,2-trichloroethyl and pentafluoroethyl; -   alkoxy: straight-chain or branched alkyl groups having 1 to 10     carbon atoms (as mentioned above) which are attached to the skeleton     via an oxygen atom (—O—); -   alkylthio: straight-chain or branched alkyl groups having 1 to 10 or     1 to 4 carbon atoms (as mentioned above) which are attached to the     skeleton via a sulfur atom (—S—); -   alkenyl: unsaturated, straight-chain or branched hydrocarbon     radicals having 2 to 4, 6 or 8 carbon atoms and a double bond in any     position, for example C₂-C₆-alkenyl such as ethenyl, 1-propenyl,     2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl,     1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl,     2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,     1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl,     1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl,     1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl,     1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl,     1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl,     1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,     1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl,     4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,     3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl,     2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl,     1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl,     4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,     1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,     1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl,     1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,     2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,     2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,     3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl,     1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl,     2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,     1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and     1-ethyl-2-methyl-2-propenyl; -   haloalkenyl: unsaturated, straight-chain or branched hydrocarbon     radicals having 2 to 8 carbon atoms and a double bond in any     position (as mentioned above), where in these groups some or all of     the hydrogen atoms may be replaced by halogen atoms as mentioned     above, in particular by fluorine, chlorine or bromine; -   alkynyl: straight-chain or branched hydrocarbon groups having 2 to     4, 6 or 8 carbon atoms and a triple bond in any position, for     example C₂-C₆-alkynyl such as ethynyl, 1-propynyl, 2-propynyl,     1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl,     2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl,     1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl,     1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl,     3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl,     1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl,     2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl,     4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl,     1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl,     2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl,     1-ethyl-3-butynyl, 2-ethyl-3-butynyl and     1-ethyl-1-methyl-2-propynyl; -   haloalkynyl: unsaturated, straight-chain or branched hydrocarbon     radicals having 2 to 8 carbon atoms and a triple bond in any     position (as mentioned above), where in these groups some or all of     the hydrogen atoms may be replaced by halogen atoms as mentioned     above, in particular by fluorine, chlorine or bromine; -   alkynyloxy: unsaturated, straight-chain or branched hydrocarbon     radicals having 3 to 8 carbon atoms and a triple bond in any     position which is not adjacent to the heteroatom (as mentioned     above), which are attached to the skeleton via an oxygen atom (—O—); -   cycloalkyl: monocyclic, saturated hydrocarbon groups having 3 to 6,     8 or 10 carbon ring members, for example C₃-C₈-cycloalkyl such as     cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and     cyclooctyl; -   5- or 6-membered heterocyclyl containing, in addition to carbon ring     members, one to three nitrogen atoms and/or one oxygen or sulfur     atom or one or two oxygen and/or sulfur atoms, for example     2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl,     3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl,     3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl,     3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl,     3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl,     4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl,     5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl,     1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl,     1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl,     1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl,     1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl,     2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl,     2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl,     2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl,     2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl,     2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl,     2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl,     2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl,     2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl,     2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl,     2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl,     2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl,     2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl,     2,3-dihydropyrazol-5-yl, 3,4-dihydro-pyrazol-1-yl,     3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl,     3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydro-     pyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl,     2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl,     2,3-dihydro-oxazol-4-yl, 2,3-dihydrooxazol-5-yl,     3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl,     3,4-dihydrooxazol-4-yl, 3,4-dihydro-oxazol-5-yl,     3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl,     3,4-dihydrooxazol-4-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl,     1,3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetra-hydropyranyl,     2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl,     2-hexahydropyrimidinyl, 4-hexahydro-pyrimidinyl,     5-hexahydropyrimidinyl, 2-piperazinyl, 1,3,5-hexa-hydrotriazin-2-yl     and 1,2,4-hexahydrotriazin-3-yl; -   5- or 6-membered heteroaryl which, in addition to carbon ring     members, may contain heteroatoms from the group consisting of     oxygen, sulfur and nitrogen: aryl as mentioned above or mono- or     bicyclic heteroaryl, for example     -   5-membered heteroaryl which contains one to four nitrogen atoms         or one to three nitrogen atom and one sulfur or oxygen atom:         5-membered heteroaryl groups which, in addition to carbon atoms,         may contain one to four nitrogen atoms or one to three nitrogen         atoms and one sulfur or oxygen atom as ring members, for example         2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl,         3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl,         4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl,         5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl,         4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl,         1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl,         1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl,         1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl         and 1,3,4-triazol-2-yl;     -   benzo-fused 5-membered heteroaryl which contains one to three         nitrogen atoms or one nitrogen atom and one oxygen or sulfur         atom: 5-membered heteroaryl groups which, in addition to carbon         atoms, contain one to four nitrogen atoms or one.to three         nitrogen atoms and one sulfur or oxygen atom as ring members and         in which two adjacent carbon ring members or one nitrogen and         one adjacent carbon ring member may be bridged by a         buta-1,3-dien-1,4-diyl group;     -   6-membered heteroaryl which contains one to three or one to four         nitrogen atoms: 6-membered heteroaryl groups which, in addition         to carbon ring members, may contain one to three or one to four         nitrogen atoms as ring members, for example 2-pyridinyl,         3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl,         2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl,         1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl; -   alkylene: divalent unbranched chains of 1 to 4 CH₂ groups, for     example CH₂, CH₂CH₂, CH₂CH₂CH₂ and CH₂CH₂CH₂CH₂; -   oxyalkylene: divalent unbranched chains of 2 to 4 CH₂ groups, where     one valency is attached to the skeleton via an oxygen atom, for     example OCH₂CH₂, OCH₂CH₂CH₂ and OCH₂CH₂CH₂CH₂; -   oxyalkyleneoxy: divalent unbranched chains of 1 to 3 CH₂ groups,     where both valencies are attached to the skeleton via an oxygen     atom, for example OCH₂O, OCH₂CH₂O and OCH₂CH₂CH₂O; -   alkenylene: divalent unbranched chains of 1 to 3 CH₂ groups and one     CH═CH group in any position, for example CH═CHCH₂, CH₂CH═CHCH₂,     CH═CHCH₂CH₂, CH₂CH═CHCH₂CH₂ and CH═CHCH₂CH₂CH₂.

With a view to the intended use of the phenylpyrimidines of the formula I, the following meanings of the substituents are particularly preferred, in each case on their own or in combination:

Preference is given, in particular, to compounds I in which R¹ is hydrogen.

Particular preference is likewise given to compounds I in which R¹ and R² independently of one another are C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl or C₂-C₆-alkenyl.

Particular preference is given to compounds of the formula I in which R¹ is C₁-C₄-alkyl and R² is hydrogen.

Particular preference is given to compounds I in which R¹ and R² together with the bridging nitrogen atom form a saturated or unsaturated 5- or 6-membered ring which may be interrupted by an ether (—O—), thio (—S—), sulfoxyl (—S[═O]—) or sulfonyl (—SO₂—) group and/or which may be substituted by one or two methyl or halomethyl groups or in which two adjacent carbon atoms are bridged by a methylene group. Substitution by one or two methyl or halomethyl groups, in particular one or two methyl groups, is particularly preferred.

Moreover, preference is given to compounds of the formula I in which R¹ and R² together form a butylene, pentylene or a pentenylene chain which may be substituted by an alkyl group, in particular a methyl group or in which two adjacent carbon atoms may be bridged by a methylene group.

Preference is furthermore given to compounds of the formula I in which R¹ and R² together form a pentylene or pentenylene chain which is substituted by a methyl group.

Particular preference is given to compounds I in which R¹ and R² together with the bridging nitrogen atom form a 3- or 4-methyl-piperidinyl group or a 2-methylpyrrolidine group.

In addition, particular preference is given to compounds I in which R³ is halogen, in particular chlorine.

Particular preference is likewise given to compounds I in which R⁴ is hydrogen, cyano, azido, C₁-C₆-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₁-C₆-haloalkyl, —ON═CR^(a)R^(b)or —NR^(c)N═CR^(a)R^(b)or —C (═NOR^(c)) NR^(a)R^(b).

Particular preference is given to compounds I in which R⁴ is cyano, —CR^(a)NOR^(b) or —ON═CR^(a)R^(b), in particular −ON═CR^(a)R^(b).

In addition, preference is given to compounds I in which R⁴ is —NH(═NH)NHR^(c), —NHC(═O)NHR^(a), —NHC(═O)R^(a), —OC(═O)R^(a), —C(═NOR^(c))NH₂ or —CR^(c)(═NNR^(a)R^(b)).

Furthermore, preference is given to compounds I in which R⁴ is —NR^(c)N═CR^(a)R^(b).

Likewise, preference is given to compounds I in which R⁴ is —C(═NOR^(c))NR^(a)R^(b), in particular —C(═NOR^(c))NH₂.

In addition, particular preference is given to compounds I in which R⁴ is C₁-C₆-alkenyl or azido.

Moreover, preference is given to compounds I in which R^(a) and R^(b) are identical or different and are hydrogen, C₁-C₆-alkyl, C₁-C₄-alkoxy, phenyl or a five- or six-membered aromatic heterocycle, where the rings may be substituted by one to three groups R^(x); among these, particular preference is given to the meanings hydrogen, alkyl, alkoxy and unsubstituted or substituted phenyl.

Particularly preferred embodiments of radicals R^(a) and R^(b) are C₁-C₄-alkyl, C₁-C₂-haloalkyl, C₁-C₄-alkoxy-C₁-C₂-alkyl, C₃-C₆-alkenyl, C₃-C₆-haloalkenyl, C₁-C₄-alkoxy, C₁-haloalkoxy, pyridyl, pyrazolyl, phenyl or benzyl, or R^(a) and R^(b) together form a butylene or pentylene chain, where the cyclic groups may be substituted by up to four substituents selected from the group consisting of halogen, C₁-C₄-alkyl, C₁-haloalkyl, C₁-C₄-alkoxy and/or C₁-C₄-alkoxy-C₁-C₂-alkyl.

A preferred embodiment of R^(c) is hydrogen.

Preference is likewise given to compounds I in which X is chlorine, fluorine, methyl, trifluoromethyl or methoxy.

Moreover, particular preference is given to compounds I in which one or two substituents X are located in the position ortho to the point of attachment of the pyrimidine ring.

In addition, particular preference is given to compounds IA

in which R¹ to R⁴ are as defined for formula I and X¹ to X⁵ are identical or different and

-   X¹ is fluorine, chlorine, C₁-C₄-alkyl, C₁-C₂-haloalkyl or     C₁-C₄-alkoxy; and -   X²,X³,X⁴,X⁵ are hydrogen or one of the groups mentioned under X¹.

Particular preference is given to compounds IA in which

-   X¹,x² are fluorine, chlorine, methyl, trifluoromethyl or methoxy; -   X³,X⁴,X⁵ are hydrogen or one of the groups mentioned under X¹ and     X².

Moreover, particular preference is given to compounds I in which X_(m), is F₅, 2-Cl, 2-F, 2-CH₃, 2-OCH₃, 2,6-Cl₂, 2,6-F₂, 2-Cl-6-F, 2-Br-6-F, 2-CH₃-4-Cl, 2-CH₃-4-F, 2-CH₃-5-F, 2-CH₃-6-F, 2-CH₃-4-OCH₃, 2-CF₃-4-F, 2-CF₃-5-F, 2-CF₃-6-F, 2-CF₃-4-OCH₃, 2-OCH₃-6-F, 2,4,6-Cl₃, 2,3,6-F₃, 2,4,6-F₃, 2,4,6-(CH₃)₃, 2,6-F₂-4-CH₃, 2,6-F₂-4-OCH₃, 2,4-F₂-6-OCH₃, 2,6-(CH₃)₂-4-OCH₃ and 2,6-(CH₃)₂-4-F.

Particular preference is given to compounds I in which X_(m) is F₅, 2,6-Cl₂, 2,6-F₂, 2-Cl-6-F, 2-CH₃-4-F, 2-CH₃-6-F, 2-CH₃-4-Cl and 2,4,6-F₃.

The compounds I are suitable for use as fungicides. They have outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them act systemically, and they can be employed in crop protection as foliar- and soil-acting fungicides.

They are especially important for controlling a large number of fungi on a variety of crop plants such as wheat, rye, barley, oats, rice, maize, grass, bananas, cotton, soya, coffee, sugar cane, grapevines, fruit species, ornamentals and vegetables such as cucumbers, beans, tomatoes, potatoes and cucurbits, and on the seeds of these plants.

Specifically, they are suitable for controlling the following plant diseases:

-   -   Alternaria species, Podosphaera species, Sclerotinia species,         Physalospora canker on vegetables and fruit,     -   Botrytis cinerea (gray mold) on strawberries, vegetables,         ornamentals and grapevines,     -   Corynespora cassiicola on cucumbers,     -   Colletotrichum species on fruit and vegetables,     -   Diplocarpon rosae on roses,     -   Elsinoe fawcetti and diaporthe citri on citrus fruits,     -   Sphaerotheca species on cucurbits, strawberries and roses,     -   Cercospora species on groundnuts, sugar beet and aubergines,     -   Erysiphe cichoracearum on cucurbits,     -   Leveillula taurica on peppers, tomatoes and aubergines,     -   Mycosphaerella species on apples and Japanese apricots,     -   Gymnosporangium yamadae, Leptothyrium pomi, Podosphaera         leucotricha and Gloedes pomigena on apples,     -   Cladosporium carpophilum on pears and Japanese apricots,     -   Phomopsis species on pears,     -   Phytophthora species on citrus fruits, potatoes, onions, in         particular Phytophthora infestans on potatoes and tomatoes,     -   Blumeria graminis (powdery mildew) on cereals,     -   Fusarium and Verticillium species on various plants,     -   Glomerella cingulata on tea,     -   Drechslera and Bipolaris species on cereals and rice,     -   Mycosphaerella species on bananas and groundnuts,     -   Plasmopara viticola on grapevines,     -   Personospora species on onions, spinach and chrysanthemums,     -   Phaeoisariopsis vitis and Spaceloma ampelina on grapefruits,     -   Pseudocercosporella herpotrichoides on wheat and barley,     -   Pseudoperonospora species on hops and cucumbers,     -   Puccinia species and Typhula species on cereals and lawn,     -   Pyricularia oryzae on rice,     -   Rhizoctonia species on cotton, rice and lawn,     -   Stagonospora nodorum and Septoria tritici on wheat,     -   Uncinula necator on grapevines,     -   Ustilago species on cereals and sugar cane, and also     -   Venturia species (scab) on apples and pears.

Moreover, the compounds I are suitable for controlling harmful fungi such as Paecilomyces variotii in the protection of materials (e.g. wood, paper, paint dispersions, fibers and fabrics) and in the protection of stored products.

The compounds I are applied by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal infection, with a fungicidally active amount of the active compounds. Application can be effected both before and after infection of the materials, plants or seeds by the fungi.

In general, the fungicidal compositions comprise from 0.1 to 95, preferably 0.5 to 90, % by weight of active compound.

When used in crop protection, the rates of application are from 0.01 to 2.0 kg of active compound per ha, depending on the nature of the desired effect.

In the treatment of seed, amounts of active compound of from 0.001 to 0.1 g, preferably 0.01 to 0.05 g, are generally required per kilogram of seed.

When used in the protection of materials or stored products, the rate of application of active compound depends on the nature of the field of application and on the desired effect. Rates of application conventionally used in the protection of materials are, for example, from 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active compound per cubic meter of material treated.

The compounds I can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular purpose; in any case, it should ensure a fine and uniform distribution of the compound according to the invention.

The formulations are prepared in a known manner, e.g. by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispersants, it also being possible to use other organic solvents as auxiliary solvents if the diluent used is water. Auxiliaries which are suitable are essentially: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. mineral oil fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) and water; carriers such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g. highly disperse silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignosulfite waste liquors and methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids and their alkali metal and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ether, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of napthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, e.g. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and water.

Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.

Granules, e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Examples of solid carriers are mineral earths, such as silicas, silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compound. The active compounds are in this case employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

The following are exemplary formulations:

-   I. 5 parts by weight of a compound according to the invention are     mixed intimately with 95 parts by weight of finely divided kaolin.     This gives a dust which comprises 5% by weight of the active     compound. -   II. 30 parts by weight of a compound according to the invention are     mixed intimately with a mixture of 92 parts by weight of pulverulent     silica gel and 8 parts by weight of paraffin oil which had been     sprayed onto the surface of this silica gel. This gives a     formulation of the active compound with good adhesion properties     (comprises 23% by weight of active compound). -   III. 10 parts by weight of a compound according to the invention are     dissolved in a mixture composed of 90 parts by weight of xylene, 6     parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1     mol of oleic acid N-monoethanolamide, 2 parts by weight of calcium     dodecylbenzenesulfonate and 2 parts by weight of the adduct of 40     mol of ethylene oxide and 1 mol of castor oil (comprises 9% by     weight of active compound). -   IV. 20 parts by weight of a compound according to the invention are     dissolved in a mixture composed of 60 parts by weight of     cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight     of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol     and 5 parts by weight of the adduct of 40 mol of ethylene oxide and     1 mol of castor oil (comprises 16% by weight of active compound). -   V. 80 parts by weight of a compound according to the invention are     mixed thoroughly with 3 parts by weight of sodium     diisobutylnaphthalene-alpha-sulfonate, 10 parts by weight of the     sodium salt of a lignosulfonic acid from a sulfite waste liquor and     7 parts by weight of pulverulent silica gel, and the mixture is     ground in a hammer mill (comprises 80% by weight of active     compound). -   VI. 90 parts by weight of a compound according to the invention are     mixed with 10 parts by weight of N-methyl-α-pyrrolidone, which gives     a solution which is suitable for use in the form of microdrops     (comprises 90% by weight of active compound). -   VII. 20 parts by weight of a compound according to the invention are     dissolved in a mixture composed of 40 parts by weight of     cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight     of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol     and 10 parts by weight of the adduct of 40 mol of ethylene oxide and     1 mol of castor oil. Pouring the solution into 100,000 parts by     weight of water and finely distributing it therein gives an aqueous     dispersion which comprises 0.02% by weight of the active compound. -   VIII. 20 parts by weight of a compound according to the invention     are mixed thoroughly with 3 parts by weight of sodium     diisobutylnaphthalene-α-sulfonate, 17 parts by weight of the sodium     salt of a lignosulfonic acid from a sulfite waste liquor and 60     parts by weight of pulverulent silica gel, and the mixture is ground     in a hammer mill. Finely distributing the mixture in 20,000 parts by     weight of water gives a spray mixture which comprises 0.1% by weight     of the active compound.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; in any case, they are intended to guarantee the finest possible distribution of the active compounds according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations can be varied within substantial ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%.

The active compounds may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active compound, or even the active compound without additives.

Various types of oils, herbicides, fungicides, other pesticides, or bactericides may be added to the active compounds, if appropriate also just prior to use (tank mix). These agents can be admixed with the agents according to the invention in a weight ratio of 1:10 to 10:1.

In the use form as fungicides, the compositions according to the invention can also be present together with other active compounds, e.g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers. Mixing the compounds I or the compositions comprising them in the use form as fungicides with other fungicides frequently results in a broader fungicidal spectrum of action.

The following list of fungicides, together with which the compounds according to the invention can be used, is intended to illustrate the possible combinations, but not to impose any limitation:

-   -   sulfur, dithiocarbamates and their derivatives, such as         Iron(III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate,         zinc ethylenebisdithiocarbamate, manganese         ethylenebisdithiocarbamate, manganese zinc         ethylenediaminebisdithiocarbamate, tetramethylthiuram disulfide,         ammonia complex of zinc (N,N-ethylenebisdithiocarbamate),         ammonia complex of zinc (N,N′-propylenebisdithiocarbamate), zinc         (N,N′-propylenebisdithiocarbamate),         N,N′-polypropylene-bis(thiocarbamoyl)disulfide;     -   nitro derivatives, such as dinitro(1-methylheptyl)phenyl         crotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,         2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl         5-nitroisophthalate;     -   heterocyclic substances, such as 2-heptadecyl-2-imidazoline         acetate, 2-chloro-N-(4′-chlorobiphenyl-2-yl)nicotinamide,         2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethyl         phthalimidophosphonothioate,         5-amino-1-[bis(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole,         2,3-dicyano-1,4-dithioanthraquinone,         2-thio-1,3-dithiolo[4,5-b]quinoxaline, methyl         1-(butylcarbamoyl)-2-benzimidazolecarbamate,         2-methoxycarbonyl-aminobenzimidazole, 2-(2-furyl)benzimidazole,         2-(4-thiazolyl)-benzimidazole,         N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide,         N-trichloromethylthiotetrahydrophthalimide,         N-trichloromethylthiophthalimide,     -   N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfodiamide,         5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,         2-thiocyanato-methylthiobenzothiazole,         1,4-dichloro-2,5-dimethoxybenzene,         4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,         pyridine-2-thiol 1-oxide, 8-hydroxyquinoline or its copper salt,         2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,         2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine 4,4-dioxide,         2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,         2-methylfuran-3-carboxanilide,         2,5-dimethylfuran-3-carboxanilide,         2,4,5-trimethylfuran-3-carboxanilide,         cyclohexyl-2,5-dimethylfuran-3-carboxamide,         N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide,         2-methylbenzanilide, 2-iodobenzanilide,         N-formyl-N-morpholine-2,2,2-trichloroethyl acetal,         piperazine-1,4-diylbis-1-(2,2,2-trichloroethyl)formamide,         1-(3,4-dichloroanilino)-i-formylamino-2,2,2-trichloroethane,         2,6-dimethyl-N-tridecylmorpholine or its salts,         2,6-dimethyl-N-cyclododecylmorpholine or its salts,         N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,         N-[3-(p-tert-butylphenyl)-2-methylpropyl]piperidine,         1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole,         1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl-methyl]-1H-1,2,4-triazole,         N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N′-imidazolylurea,         1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone,         1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,         (2RS,3RS)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiran-2-ylmethyl]-1H-1,2,4-triazole,         α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,         5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine,         bis(p-chlorophenyl)-3-pyridinemethanol,         1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene,         1,2-bis-(3-methoxycarbonyl-2-thioureido)benzene,     -   strobilurins such as methyl         E-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]phenyl}-3-methoxyacrylates,         (E)-2-(methoxyimino)-N-methyl-2-[α-(2,5-xylyloxy)-o-tolyl]acetamide,         {2-[6-(2-chlorophenoxy)-5-fluoropyrimidin-4-yloxy]phenyl}-(5,6-dihydro-1,4,2-dioxazin-3-yl)methanone         O-methyloxime, methyl         (E)-methoxyimino[α-(o-tolyloxy)-o-tolyl]acetate,         (E)-2-(methoxyimino)-N-methyl-2-(2-phenoxyphenyl)acetamide,         (2E)-2-(methoxyimino)-2-{2-[(3E,5E,6E)-5-(methoxyimino)-4,6-dimethyl-2,8-dioxa-3,7-diazanona-3,6-dien-1-yl]phenyl}-N-methylacetamide,         methyl         (E)-3-methoxy-2-{2-[6-(trifluoromethyl)-2-pyridyloxymethyl]phenyl}acrylate,         methyl         N-{2-[1-(4-chlorophenyl)-1H-pyrazol-3-yloxymethyl]phenyl}-(N-methoxy)carbamate,         methyl         (E)-methoxyimino-{(E)-α-[1-(α,α,α-trifluoro-m-tolyl)ethylideneaminooxy]-o-tolyl}acetate,     -   anilinopyrimidines such as         N-(4,6-dimethylpyrimidin-2-yl)-aniline,         N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]aniline,         N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline,     -   phenylpyrroles such as         4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile,     -   cinnamides such as         3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloylmorpholine,         3-(4-fluorophenyl)-3-(3,4-dimethozyphenyl)acryloylmorpholide,     -   and a variety of fungicides such as dodecylguanidine acetate,         1-(3-bromo-6-methoxy-2-methylphenyl)-1-(2,3,4-trimethoxy-6-methylphenyl)methanone,         3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide,         hexachlorobenzene, methyl         N-(2,6-dimethylphenyl)-N-(2-furoyl)-DL-alaninate,         DL-N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl)alanine methyl         ester,         N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-amino-butyrolactone,         DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanine methyl ester,         5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,         3-(3,5-dichlorophenyl)-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,         3-(3,5-dichlorophenyl)-1-isopropylcarbamoylhydantoin,         N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,         2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]acetamide,         1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole,         2,4-difluoro-α-(1H-1,2,4-triazolyl-1-methyl)benzhydryl alcohol,         N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine,         1-((bis(4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4-triazole-5-chloro-2-cyano-4-n-tolylimidazole-1-sulfodimethylamide,         3,5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide.

SYNTHESIS EXAMPLES

With due modification of the starting compounds, the protocols shown in the synthesis examples below were used for obtaining further compounds I. The resulting compounds, together with physical data, are listed in Table 1 below.

Example 1 Preparation of [6-chloro-2-(N′-isopropylidene-hydrazino)-5-(2,4,6-trifluorophenyl)pyrimidine-4-yl]-((S)-1-tri-fluoromethylethyl)amine [I-1]

0.16 g (2.2 mmol) of acetone oxime was added to 0.065 g (2.4 mmol) of sodium hydride in 10 ml of dimethylformamide (DMF). The mixture was stirred at 20-25° C. for 1 hour, after which 1.0 g (2.2 mmol) of [6-chloro-2-methanesulfonyl-5-(2,4,6-trifluorophenyl)pyrimidin-4-yl]-((S)-1-trifluoromethylethyl)amine (abbr. sulfone 1) was added. After a further 14 hours of stirring at 20-25° C., the mixture was poured into water and extracted with dichloromethane. The combined organic phases were washed with water, then dried and finally freed from the solvent. This gave 0.6 g of the title compound of m.p. 157-159° C.

Example 2 Preparation of [6-chloro-2-methoxy-5-(2,4,6-trifluorophenyl)pyrimidin-4-yl]-((S)-1-trifluoromethylethyl)amine [I-24]

294 mg (1.30 mmol) of sodium methoxide (90% in methanol) were added to a solution of 282 mg (0.65 mmol) of sulfone 1 in 4 ml of anhydrous DMF. The mixture was stirred at 20-25° C. for 16 hours and then diluted with MTBE, washed with water and dried. Distillative removal of the solvent and chromatography on silica gel gave 0.14 g of the title compound of m.p. 121-129° C.

Example 3 Preparation of [6-chloro-2-methylsulfanyl-5-(2,4,6-trifluorophenyl)pyrimidin-4-yl]isopropylamine [I-30]

70 mg (1.0 mmol) of sodium thiomethoxide, dissolved in 3 ml of anhydrous THF, were added to a solution of 216 mg (0.5 mmol) of [6-chloro-2-methanesulfonyl-5-(2,4,6-trifluorophenyl)pyrimidin-4-yl]isopropylamine (abbr. sulfone 2) in 2 ml of anhydrous DMF. The mixture was stirred at 20-25° C. for 16 hours and then diluted with MTBE, washed with water and dried. Distillative removal of the solvent and chromatography on silica gel gave 0.21 g of the title compound of m.p. 112-116° C.

Example 4 Preparation of [6-chloro-2-hydrazino-5-(2,4,6-trifluorophenyl)pyrimidin-4-yl]-((S)-1-trifluoromethylethyl)amine

An ethanolic solution of 0.5 g (1.15 mmol) of sulfone 1 and 0.13 g (2.54 mmol) of hydrazine hydrate was stirred at 20-25° C. for 2 hours. The solvent was distilled off and the residue was digested with diisopropyl ether, and the residue was then filtered off and washed with diisopropyl ether/hexane 1:1.

Example 5 Preparation of [6-chloro-2-[N′-(1-trifluoromethylethylidene)hydrazino]-5-(2,4,6-trifluorophenyl)pyrimidin-4-yl]-((S)-1-trifluoromethylethyl)amine [I-56]

A solution of 0.8 g (2.07 mmol) of the hydrazide from Ex. 4 and 0.28 g (2.49 mmol) of 1,1,1-trifluoroacetone in acetonitrile was stirred at 20-25° C. for 16 hours. The precipitate was filtered off; the filtrate gave, after chromatography on silica gel (CH:MTBE 95:5), 0.3 g of the title compound of m.p. 205-207° C.

Example 6 Preparation of [6-chloro-2-(N-phenylhydrazino)-5-(2,4,6-trifluorophenyl)pyrimidin-4-yl]-((S)-1-trifluoromethylethyl)amine [I-62]

An ethanolic solution of 0.5 g (1.15 mmol) of sulfone 1 and 0.15 g (1.38 mmol) of phenylhydrazine was refluxed for 14 hours. Cooling, distillative removal of the solvent and chromatography on silica gel (cyclohexane:methyl tert-butyl ether [MTBE] 95:5) gave 0.36 g of the title compound.

Example 7 Preparation of [2-azido-6-chloro-5-(2,4,6-trifluorophenyl)pyrimidin-4-yl]-((S)-1-trifluoromethylethyl)amine [I-66]

A solution of 0.5 g (1.15 mmol) of sulfone 1 and 0.11 g (1.62 mmol) of sodium azide in acetonitrile was refluxed for 2 hours. Cooling, distillative removal of the solvent and digestion of the residue with water gave 0.33 g of the title compound of m.p. 152-154° C.

Example 8 Preparation of 6-chloro-5-(2-chloro-6-fluorophenyl)-N¹-isopropyl-N²-phenylpyrimidine-2,4-diamine [I-69]

At −70° C., 0.62 g (6.6 mmol) of aniline was added to a suspension of 2.9 g of butyllithium (15% solution in hexane) in 15 ml of tetrahydrofuran [THF], and the mixture was then stirred at −70° C. for 1 hour. 1.0 g (2.64 mmol) of [6-chloro-5-(2-chloro-6-fluorophenyl)-2-methanesulfonylpyrimidin-4-yl]isopropylamine (abbr. sulfone 3) was added, and the mixture was then warmed to 20-25° C. The reaction mixture was poured into ice-water and acidified with hydrochloric acid. The mixture was extracted with 2×40 ml of MTBE, and the combined organic phases gave, after drying and distillative removal of the solvent, 1.0 g of the title compound.

Example 9 Preparation of 4-chloro-6-((S)-1-trifluoromethylethyl-amino)-5-(2,4,6-trifluorophenyl)pyrimidin-2-carbonitrile [I-73]

A solution of 0.5 g (1.15 mmol) of sulfone 1 and 0.36 g (2.31 mmol) of tetraethylammonium cyanide in dichloromethane was stirred at 20-25° C. for 20 hours. Distillative removal of the solvent and chromatography on silica gel (cyclohexane [CH]:MTBE 9:1) gave 0.18 g of the title compound of m.p. 134-136° C.

Example 10 Preparation of 4-chloro-5-(2-chloro-6-fluorophenyl)-6-isopropylaminopyrimidine-2-carbonitrile [I-74]

A solution of 1.0 g (2.63 mmol) of sulfone 3 and 0.21 g (3.16 mmol) of potassium cyanide in acetonitrile was stirred at 20-25° C. for 5 days. The solvent was distilled off and the residue was digested with MTBE:ethyl acetate [EA] 9:1. Filtration and concentration of the filtrate gave 0.61 g of the title compound of m.p 186-188° C.

TABLE I

Phys. data No. R¹ R² R³ R⁴ X¹ X² X³ X⁴ X⁵ (m.p. [° C.]) I-1

H Cl

F F H F H 157-159 I-2

H Cl

F F H F H 88-92 I-3

H Cl

F F H F H 176-179 I-4

H Cl

F F H F H 151-155 I-5

H Cl

F F H F H 110-112 I-6

H Cl

F F H F H 145-146 I-7

H Cl

F F H F H 139-141 I-8

H Cl

F F H F H 350 I-9

H Cl

F F H F H 84-86 I-10

H Cl

F F H F H 68-70 I-11

H Cl

F F H F H 87-90 I-12

H Cl

F F H F H 137-139 I-13

H Cl

Cl F H H H 147-149 I-14

H Cl

F F H F H oil I-15

H Cl

Cl F H H H 165-168 I-16

H Cl

F F H F H oil I-17

H Cl

Cl F H H H 110-112 I-18

H Cl

Cl F H H H 125-127 I-19

H Cl

F F H F H 116-117 I-20

H Cl

Cl F H H H  98-100 I-21

H Cl —O—C(CH₃)₃ Cl F H H H 118-121 I-22

H Cl

Cl F H H H 108-111 I-23

H Cl

F F H F H 129-131 I-24

H Cl

F F H F H 121-129 I-25

H Cl

F F H F H 147-149 I-26

H Cl

F F H F H 159-161 I-27

Cl

Cl F H H H 164-169 I-28

Cl

F F H F H oil I-29

Cl

F F H F H oil I-30

H Cl

F F H F H 112-116 I-31

H Cl

Cl F H H H 106-110 I-32

H Cl

F F H F H oil I-33

H Cl

Cl F H H H 104-108 I-34

H Cl

F F H F H 95-98 I-35

H Cl

Cl F H H H oil I-36

H Cl

F F H F H oil I-37

H Cl

Cl F H H H 111-113 I-38

H Cl

Cl F H H H oil I-39

H Cl

Cl F H H H 94-96 I-40

H Cl

F F H F H oil I-41

H Cl

Cl F H H H 114-117 I-42

H Cl

F F H F H oil I-43

H Cl

F F H F H 68-69 I-44

H Cl —S—CH(CH₃)₂ F F H F H 73-76 I-45

H Cl —S—CH₂CH₂CH₃ F F H F H oil I-46

H Cl

F F H F H oil I-47

H Cl

F F H F H 64-65 I-48

H Cl

F H H H H 124-126 I-49

Cl

F H H H H oil I-50

Cl

F H H H H oil I-51

H Cl

F H H H H oil I-52

Cl

F H H H H oil I-53

H Cl

F H H H H 135-137 I-54

H Cl

F F H F H oil I-55

H Cl

F F H F H oil I-56

H Cl

F F H F H 205-207 I-57

H Cl

F F H F H 185-187 I-58

H Cl

F F H F H 84-87 I-59

H Cl

F F H F H 138-140 I-60

H Cl

F F H F H 205-208 I-61

H Cl

F F H F H 152-155 I-62

H Cl

F F H F H oil I-63

H Cl

F F H F H 132-134 I-64

H Cl

F F H F H 126-128 I-65

H Cl

F F H F H oil I-66

H Cl

F F H F H 152-154 I-67

H Cl

Cl F H H H 91-94 I-68

H Cl

Cl F H H H 151-153 I-69

H Cl

Cl F H H H oil I-70

H Cl

Cl F H H H oil I-71

Cl

Cl F H H H 107-109 I-72

Cl

Cl F H H H oil I-73

H Cl

F F H F H 134-136 I-74

H Cl

Cl F H H H 186-188 I-75

H Cl

F F H F H 83-85 I-76

H Cl

Cl F H H H 87-90 I-77

CH₃ Cl

H H F H H 75-77 I-78

Cl

Cl F H H H oil I-79

Cl

Cl F H H H oil I-80

Cl

Cl F H H H oil I-81

H Cl

F F H F H 94-96 I-82

H Cl

F F H F H  91 I-83

H Cl

F F H F H 180 I-84

H Cl

F F H F H 157 I-85

H Cl

F F H F H 159 I-86

H Cl

F F H F H 113-118 I-87

H Cl

F F H OCH₃ H oil I-88

Cl

F F H F H oil I-89

Cl

F F H F H oil I-90

Cl

F F H F H oil I-91

Cl

F F H F H oil I-92

Cl

Cl F H H H oil I-93

Cl

F H H CH₃ H oil I-94

Cl

CH₃ H H CH₃ H oil I-95

H Cl

F F H F H  99-105 I-96

H Cl

F F H F H 120-123 I-97

H Cl

F F H F H 106-109 I-98

H Cl

F F H F H 120-123 I-99

H Cl —OH F F H F H  84-101 I-100

H Cl

F F H F H 156-158 I-101

H Cl

F F H F H oil I-102

H Cl

Cl F H H H oil I-103

H Cl

Cl F H H H oil I-104

H Cl

Cl F H H H oil I-105

H Cl

Cl F H H H oil I-106

H Cl

Cl F H H H oil I-107

H Cl

Cl H H F H 127 I-108

H Cl

F F H OCH₃ H oil I-109

Cl

F F H F H  98-102 I-110

Cl

F F H F H oil I-111

Cl

F F H F H oil I-112

Cl

F F H F H oil I-113

Cl

F F H F H 123-125 I-114

H Cl

F F H F H 133 I-115

H Cl

F F H F H 155 I-116

H Cl

F F H F H 146 I-117

H Cl

F F H F H 126-129 I-118

Cl

F F H F H oil I-119

Cl

F F H F H oil I-120

Cl

F F H F H oil I-121

Cl

F F H F H 107-109 I-122

Cl

F F H F H oil I-123

Cl

F F H F H 141-149 I-124

Cl

F F H F H 179-188 I-125

Cl

F F H F H 181-191 I-126

Cl

F F H F H oil I-127

Cl

F F H F H oil I-128

Cl

F F H F H oil I-129

Cl

F F H F H oil I-130

Cl CN F F H F H 89-98 I-131

Cl

F F H F H 82-90 I-132

Cl

F F H F H oil I-133

Cl

F F H F H oil I-134

Cl

F F H F H oil I-135

Cl

F F H F H  96 I-136

Cl

F F H F H  72 I-137

Cl

F F H F H 125 I-138

Cl

F F H F H 119 I-139

Cl

F F H F H 154 I-140

Cl

CH₃ CH₃ H H H oil I-141

Cl

F F H F H  98-102 I-142

CH₃

F F H F H oil I-143

Cl

F F H F H oil I-144

Cl

F F H F H oil I-145

Cl

F F H F H oil I-146

Cl

F F H F H  70 I-147

Cl

F F H F H oil I-148

Cl

F F H F H  96 I-149

Cl

F H H F H 128 I-150

OCH₃

F F H F H oil I-151

OCH₃

CH₃ H H F H 105 I-152

OCH₃

F F H F H oil I-153

OCH₃

F F H F H oil I-154

OCH₃

F F H F H oil I-155

OCH₃

F H H F H oil I-156

Cl

F F H F H 239-242 I-157

Cl

F F H F H oil I-158

Cl

F F H F H oil I-159

OCH₃

F F H F H 106-124 I-160

Cl

F F H F H oil I-161

Cl

F F H F H oil I-162

Cl

F F H F H 117 I-163

Cl

F F H F H oil I-164

Cl

F F H F H oil I-165

Cl

F F H F H oil I-166

Cl

F F H F H oil I-167

Cl

F F H F H oil I-168

Cl

F F H F H oil I-169

Cl

F F H F H oil I-170

Cl

F F H F H oil I-171

Cl

F F H F H oil I-172

Cl

F F H F H oil I-173

Cl

F F H F H oil I-174

Cl

F F H F H oil I-175

Cl

F F H F H oil I-176

Cl

F F H F H oil I-177

Cl

F F H F H oil I-178

Cl

F F H F H oil I-179

Cl

F F H F H oil I-180

Cl

F F H F H oil I-181

Cl

F F H F H oil I-182

Cl

F F H F H oil I-183

Cl

F F H F H oil I-184

Cl

F F H F H oil I-185

Cl

F F H F H oil I-186

Cl

F F H F H oil I-187

Cl

F F H F H oil I-188

Cl

CH₃ CH₃ H H H oil I-189

Cl

F F H OCH₃ H oil I-190

Cl

F F H OCH₃ H oil I-191

Cl

F F H OCH₃ H oil I-192

Cl

F F H OCH₃ H oil I-193

Cl

F F H OCH₃ H oil I-194

Cl

Cl F H H H 109 I-195

Cl

Cl F H H H oil I-196

Cl

Cl F H H H oil I-197

Cl

Cl F H H H 126 I-198

Cl

Cl F H H H 164-169 I-199

Cl

Cl F H H H oil I-200

Cl

Cl F H H H oil I-201

Cl

Cl F H H H 107-109 I-202

Cl

Cl F H H H oil I-203

Cl

Cl F H H H oil I-204

Cl

Cl F H H H oil I-205

Cl

Cl F H H H oil I-206

Cl

Cl F H H H oil I-207

Cl

F H H H H oil I-208

Cl

F H H CH₃ H oil I-209

Cl

F H H CH₃ H 136 I-210

Cl

F H H CH₃ H oil I-211

Cl

F H H CH₃ H 95-97 I-212

OCH₃

F H H CH₃ H oil I-213

Cl

F H H CH₃ H oil I-214

Cl

F H H CH₃ H oil I-215

Cl

F H H CH₃ H 148 I-216

Cl

F H H H H oil I-217

Cl

F H H H H oil I-218

Cl

H H F H H 75-77 I-219

H Cl

F F H F H 205-207 I-220

H Cl

F F H F H 185-187 I-221

H Cl

F F H F H 84-87 I-222

H Cl

F F H F H 138-140 I-223

H Cl

F F H F H oil I-224

H Cl

F F H F H 137-139 I-225

H Cl

F F H F H oil I-226

H Cl

F F H F H oil I-227

H Cl

F F H F H oil I-228

H Cl

F F H F H 112-116 I-229

H Cl

F F H F H oil I-230

H Cl

F F H F H 95-98 I-231

H Cl

Cl F H H H 91-94 I-232

H Cl

Cl F H H H 151-153 I-233

H Cl

Cl F H H H oil I-234

H Cl

Cl F H H H oil I-235

H Cl

Cl F H H H 147-149 I-236

H Cl

Cl F H H H 165-168 I-237

H Cl

Cl F H H H 110-112 I-238

H Cl

Cl F H H H 125-127 I-239

H Cl

Cl F H H H 118-121 I-240

H Cl

Cl F H H H  98-100 I-241

H Cl

Cl F H H H 108-111 I-242

H Cl

Cl F H H H 106-110 I-243

H Cl

Cl F H H H oil I-244

H Cl

Cl F H H H 111-113 I-245

H Cl

Cl F H H H 94-96 I-246

H Cl

Cl F H H H oil I-247

H Cl

Cl F H H H 114-117 I-248

H Cl

Cl F H H H 104-108 I-249

H Cl

Cl F H H H 186-188 I-250

H Cl

F H H H H oil I-251

H Cl

F H H H H 124-126 I-252

H Cl

F H H H H 135-137 I-253

H Cl

F F H F H 139-141 I-254

H Cl

F F H F H 157-159 I-255

H Cl

F F H F H 88-92 I-256

H Cl

F F H F H 176-179 I-257

H Cl

F F H F H 110-112 I-258

H Cl

F F H F H 350 I-259

H Cl

F F H F H 68-70 I-260

H Cl

F F H F H 145-146 I-261

H Cl

F F H F H 151-155 I-262

H Cl

F F H F H 87-90 I-263

H Cl

F F H F H 84-86 I-264

H Cl

F F H F H oil I-265

H Cl

F F H F H oil I-266

H Cl

F F H F H 152-155 I-267

H Cl

F F H F H 205-208 I-268

H Cl

F F H F H oil I-269

H Cl

F F H F H oil I-270

H Cl

F F H F H 132-134 I-271

H Cl

F F H F H 126-128 I-272

H Cl

F F H F H oil I-273

H Cl

F F H F H 152-154 I-274

H Cl

F F H F H 137-146 I-275

H Cl

F F H F H 121-129 I-276

H Cl

F F H F H 147-149 I-277

H Cl

F F H F H 159-161 I-278

H Cl

F F H F H 116-117 I-279

H Cl

F F H F H 129-131 I-280

H Cl

F F H F H oil I-281

H Cl

F F H F H 68-69 I-282

H Cl

F F H F H 73-76 I-283

H Cl

F F H F H oil I-284

H Cl

F F H F H oil I-285

H Cl

F F H F H 64-65 I-286

H Cl

F F H F H 83-85 I-287

H Cl

F F H F H 134-136 I-288

H Cl

Cl F H H H 87-90 I-289

H Cl

F F H F H  82 I-290

H Cl

F F H F H 130 I-291

H Cl

F F H F H  69 I-292

H Cl

F F H F H 120 I-293

H Cl

F F H F H  87 I-294

H Cl

F F H F H  97 I-295

H Cl

F F H F H 140 I-296

H Cl

F F H F H 175 I-297

H Cl

F F H F H 157 I-298

H Cl

F F H F H oil I-299

H Cl

F F H F H 108-112 The R⁴ groups are attached to the pyrimidine skeleton via the free valencies. Owing to their C═C, C═N and N═N double bonds, the groups R⁴ can be present as E/Z isomer mixtures.

EXAMPLES OF THE ACTIVITY AGAINST HARMFUL FUNGI

The fungicidal activity of the compounds of the formula I was demonstrated by the following experiments:

-   The active compounds were formulated, separately or together, as a     10% strength emulsion in a mixture of 70% by weight of     cyclohexanone, 20% by weight of Nekanil® LN (Lutensol® AP6, wetting     agent having emulsifying and dispersing action based on ethoxylated     alkylphenols) and 10% by weight of Wettol® EM (nonionic emulsifier     based on ethoxylated castor oil) and diluted with water to the     desired concentration.

Use Example 1 Activity against Septoria Leaf Blotch of Wheat (Septoria tritici)

Leaves of potted wheat seedlings of the cultiva “Riband” were sprayed to runoff point with an aqueous preparation of active compound which had been prepared from a stock solution comprising 10% of active compound, 85% of cyclohexanone and 5% of emulsifier. 24 hours after the spray coating had dried on, the seedlings were inoculated with an aqueous spore suspension of Septoria tritici. The suspension contained 2.0×10⁶ spores/ml. The test plants were then placed in a greenhouse at temperatures between 18 and 22° C. and a relative atmospheric humidity close to 100%. After 2 weeks, the extent of the development of the disease was determined visually in % infection of the total leaf area.

In this test, the plants which had been treated with 250 ppm of the active compounds Nos. 1, 12 to 15, 18, 19, 21, 24 to 26, 30, 32, 33, 54, 55, 60, 61 to 65, 86, 160, 223, 224, 226, 228, 235 to 239, 248, 254, 264, 265, 269, 270, 271, 272 and 275 to 278 of Table I showed an infection of at most 7%, whereas the untreated plants were 90% infected.

Use Example 2 Activity against Net Blotch of Barley (Pyrenophora teres)

Leaves of potted barley seedlings of the cultivar “Igri” were sprayed to runoff point with an aqueous preparation of active compound which had been prepared from a stock solution comprising 10% of active compound, 85% of cyclohexanone and 5% of emulsifier and, 24 hours after the spray coating had dried on, inoculated with an aqueous spore suspension of Pyrenophora [syn. Drechslera] teres, the net blotch pathogen. The test plants were then placed in a greenhouse at temperatures between 20 and 24° C. and at 95-100% relative atmospheric humidity. After 6 days, the extent of the development of the disease was determined visually in % infection of the total leaf area.

In this test, the plants which had been treated with 250 ppm of the active compounds Nos. 1, 55, 60, 64, 73, 88, 130, 134, 160, 163, 165, 168, 171, 185, 186, 254, 255, 265, 267, 271, 274, 276, 277, 278 and 287 of Table I showed an infection of not more than 15%, whereas the untreated plants were 100% infected.

Use Example 3 Protective Activity against Mildew of Cucumber Caused by Sphaerotheca fuliginea

Leaves of potted cucumber seedlings of the cultivar “Chinese Snake” were, at the cotyledon stage, sprayed to runoff point with an aqueous preparation of active compound which had been prepared from a stock solution comprising 10% of active compound, 85% of cyclohexanone and 5% of emulsifier 20 hours after the spray coating had dried on, the plants were inoculated with an aqueous spore suspension of mildew of cucumber (Sphaerotheca fuliginea). The plants were then cultivated in a greenhouse at 20-24° C. and 60-80% relative atmospheric humidity for 7 days. The extent of the mildew development was then determined visually in % infection of the cotyledon area.

In this test, the plants which had been treated with 250 ppm of the active compounds Nos. 86, 88, 100, 121, 130, 141, 160, 163, 168, 171, 185, 186, 189, 206, 220, 249, 253 to 261, 265, 266, 271, 273, 275, 276, 287 and 299 of Table I showed an infection of not more than 10%, whereas the untreated plants were 85% infected. 

1. A 5-phenylpyrimidine of the formula I

where the substituents and the index are as defined below: R¹ is C₁—C₆-alkyl, C₁—C₆-haloalkyl, C₃—C₆cycloalkyl, C₃—C₆-halo-cycloalkyl, C₂—C₆-alkenyl, C₂—C₆-haloalkenyl, C₂—C₆-alkynyl or C₂—C₆-haloalkynyl, R² is hydrogen or a group as defined for R¹, or R¹ and R² together with the nitrogen atom to which they are attached may also form a saturated or unsaturated five- or six-membered ring which may be interrupted by an ether- (—O—), thio- (—S—), sulfoxyl- (—S[═O]—) or sulfenyl- (—SO₂—) group and/or may be substituted by one to four groups R^(a) and/or R^(b); R^(a), R^(b) independently of one another are hydrogen, C₁—C₆-alkyl, C₂—C₈-alkenyl, C₂—C₈-alkynyl, C₁—C₆-haloalkyl, C₁—C₆-alkoxy, C₁—C₆-haloalkoxy, C₃—C₁₀-cycloalkyl, phenyl or a five- to ten-membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group consisting of O, N and S, where the cyclic radicals may be partially or fully substituted by the following groups R^(x); or R^(a) and R^(b) together, via an alkylene or alkenylene chain with the bridging atom, may also form a saturated or unsaturated 5- or 6- membered ring; R^(x) independently of one another are cyano, nitro, amino, aminocarbonyl, aminothiocarbonyl, halogen, hydroxyl, C₁—C₆-alkyl, C₁—C₆-haloalkyl, C₁—C₆-alkylcarbonyl, C₁—C₆-alkylsulfonyl, C₁—C₆-alkylsulfoxyl, C₃—C₆-cycloalkyl, C₁—C₆-alkoxy, C₁—C₆-haloalkoxy, C₁—C₆-alkyloxycarbonyl, C₁—C₆-alkylthio, C₁—C₆-alkylamino, di-C₁—C₆-alkylamino, C₁—C₆-alkylaminocarbonyl, di-C₁—C₆-alkylaminocarbonyl, C₁—C₆-alkylaminothiocarbonyl, di-C₁—C₆-alkylaminothiocarbonyl, C₂—C₆-alkenyl, C₂—C₆-alkenyloxy, phenyl, phenoxy, benzyl, benzyloxy, 5- or 6-membered heterocyclyl, 5- or 6-membered hetaryl, 5 -or 6-membered hetaryloxy, C(═NOR^(α))—OR^(β) or OC(R^(α))₂—C(R^(β))═NOR^(β)where the cyclic groups for their part are unsubstituted or substituted by one to three radicals R^(y); R^(y) is cyano, nitro, halogen, hydroxyl, amino, aminocarbonyl, aminothiocarbonyl, C₁—C₆-alkyl, C₁—C₆-haloalkyl, C₁—C₆-alkylsulfonyl, C₁—C₆-alkylsulfoxyl, C₃—C₆-cycloalkyl, C₁—C₆-alkoxy, C₁—C₆-haloalkoxy, C₁—C₆-alkoxycarbonyl, C₁—C₆-alkylthio, C₁—C₆-alkylamino, di-C₁—C₆-alkylamino, C₁—C₆-alkylaminocarbonyl,di-C₁—C₆-alkylaminocarbonyl, C₁—C₆-alkylaminothiocarbonyl, di-C₁—C₆-alkylaminothiocarbonyl, C₂—C₆-alkenyl, C₂—C₆-alkenyloxy, C₂—C₆-cycloalkyl, C₃—C₆-cycloalkenyl, phenyl, phenoxy, phenylthio, benzyl, benzyloxy, 5- or 6-membered heterocyclyl, 5 - or 6-membered hetaryl, 5- or 6-membered hetaryloxy or C(═NOR^(α))—OR^(β); R^(α), R^(β) are hydrogen or C₁—C₆-alkyl; R³ is halogen, cyano or C₁—C₆-alkyl; R⁴ is cyano; X is halogen, C₁—C₆-alkyl, C₁—C₆-alkoxy or C₁—C₆-haloalkyl; and m is an integer from 1 to
 5. 2. A 5-phenylpyrimidine of the formula I

where the substituents and the index are as defined below: R¹ is C₁—C₆-alkyl, C₁—C₆-haloalkyl, C₃—C₆-cycloalkyl, C₃—C₆-halocycloalkyl, C₂—C₆-alkenyl, C₂—C₆-haloalkenyl, C₂—C₆-alkynyl or C₂—C₆-haloalkynyl, R² is hydrogen or a group as defined for R¹, or R¹ and R² together with the nitrogen atom to which they are attached may also form a saturated or unsaturated five- or six-membered ring which may be interrupted by an oxygen atom and which may carry a C₁—C₆-alkyl substituent or in which two adjacent carbon ring members may be bridged by a C₁—C₄-alkylene group; R³ is halogen or cyano; R⁴ is cyano; X is halogen, C₁—C₆-alkyl, C₁—C₆-alkoxy or C₁—C₆-haloalkyl; and m is an integer from 1 to
 5. 